Halogen derivative of anthraquinone and process of making same.



' UNITED STATES? PATENT OFFICE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISOHE ANILIN AND SODA FABRIK, QF LUDWIGSHAFEN, GERMANY.

HALOGEN DERIVATIVE OF ANTHRAQUlNONE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of LettersPatent No. 631,606, dated August 22, 1899.

Application filed April 12,1899. Serial No- 712,'763. (No specimens.)

To all whom, it may concern.-

. Be it known that I, OSCAR BALLY, doctor of philosophy, a citizen of the Swiss Republic, residing at Mannheim, in the Grand Duchy of Baden and Empire of Germany, have invented new and useful Improvements in the Manufacture of Halogen Derivatives of Alphylated Amido-Anthraquinones, (for which application for patent was made in Germany, No. B 23,556, October'15, 1898,) of which the following is a specification;

- Itis known that if 1.5-di-ortho-nitro-anthraquinone beboiledIwith an alin a product is oband dissolves in hot alcohol, giving a purple solution. (See Romer, Bertchte of the German Chemical Society, Vol. 16, page 363.) If, on the one hand, other primary aromatic amins be used instead of anilin, or, on the other hand, isomeric di-nitro-anthraquinones be employed,analogous compounds are obtained, and these appear to be chemically alphylated amido-anthraquinones. For the sake of convenience I give below an example of the method by which these alphylated di-amidoanthraquinones can be obtained, but my invention consists in converting the said alphylated-amido-anthraquinones into halogen derivativesnamely, bromin or chlorin derivatives. The bromin derivatives are obtained by treating the alphylated amido-anthraquinones in a suitable solvent with an excess of bromin. The chlorin derivatives are obtained in a similar'way,but using chlorin.

The essential characteristic of my new products, these halogen derivatives of alphylated amido-anthraquinones, is that the halogens in the molecule possess a very high capacity for entering into reactions, and consequently the new compounds are susceptible of treatment in various ways to yield new products, many of which are valuable coloring-matters.

The following examples will serve to further illustrate the manner in which my invention can be carried into practical efiect. The parts are by weight. Example 1 Production ofalp hylated amtdo-I anthraqutnone from 1.5 dtnttroanthraquinone.Mix together about ten parts of 1.5- dinitro-anthraquinone and one hundred (100) parts of anilin. Heat the mixture for from (500) parts of alcohol.

three to four hours, so that it boils. A vigorous reaction takes place at first, but the heating is continued until this has left off. Allow the mixture to cool. The alphylated amido-anthraquinone crystallizes out. .Work up in any suitable way. Instead of using the pure 1.5-dinitro-anthraquinone in the above example crude dinitro-anthraquinone, obtained by nitrating anthraquinone, can be employed, and in an analogous manner the isolated isomeric dinitro-anthraquinones. can be used when the corresponding alphylated amidoanthraquin'ones are obtained. tained which crystallizes in deep-red needles Example 2: Production of a new bromin derivative from the alphylated amide-anthraqutnone obtained from J.5 dtnttro-anthraqutnone and antltn.Dissolve about ten (10) parts of the alphylated amido-anthraquinone Obtained according to the above example in about six hundred (600) parts of carbon bisulfid. Heat the mixture to facilitate solution. Then add about twenty (20). parts of bromin, and boil the mixture till no further evo lution of hydro-bromic-acid can be noticed. Distil off the carbon bisulfid until only about one hundred and fifty (150) parts remain and dilute the residue with about five hundred The new bromin derivative separates as a crystalline precipitate. Filter and dry.

Example 3: Production of a new bromin derivative from the alphylated amtdo-anthra- '1 qu'tnone obtained from 1.delinttraanthraqutnone and para-tolutdtn.-Suspend about ten (10) parts of the said alphylated amide-anthraquinone in about one hundred (100) parts of glacial acetic acid and add at the ordinary temperature twenty (20) parts of bromin. Stir the'mixtu re thoroughly and warm gently for some time. Allow to cool. The bromin derivative separates out. Collect by filtering.

Example 4: Production of new chlortn dertuattues of the alphylated amtdo-anthraqutnone from 1. 5-cltnttro-anthraqutnone and antltn.-Make a suspension of about ten (10) parts of the said alphylated amido-anthraquino'ne in about one hundred (100) parts of glacial acetic acid and treat the mixture at the ordinary temperature with gaseous chlorin until the evolution of hydrochloric acid ceases. Allow the mixture to stand for about twelve hours. A portion of the product of reaction (Product A) separates out. This generally contains some unchanged alphylated product. The solution that remains contains higher chlorinated derivatives of the alphylated product, (Product B.) Collect the separated chlorinated product by filtering, and to the filtrate add water to precipitate the higher chlorinated product. Collect this in the usual way.

In the following table I describe the properties of various halogen derivatives obtained by treating the various alphylated amido-anthraquinones herein indicated in the manner all mixtures of various highly-substituted halogen derivatives. They all possess the characteristic property that on treatment with aromatic amins they are converted into valuable coloring-matters, which in the form of their sulfoacids dye unmordanted or chromemordanted wool, giving valuable green shades. The production of these green coloring-matters forms the subject-matter of a separate application for Letters Patent.of even date herewith, filed April 12, 1899, Serial No. 712,762. The further properties of my new halogen derivatives of the alphylated amido-anthraquinones can be seen from described in the above examples. These are the table referred to.

801mm on in a1 0 OhOL Solution in glacial acetic solu tion in Color of the Solution in c o n ce n powder. benzene. trated snl= Cold. Hot. Cold. Hot.

Bromin derivative from coudeu- Violet to red Hardly solu Somewhat Rathersolu- Easily solu Readily sol- Olive green.

sation product of lj-dinitro-an brown. ble. more soluble. ble. uble. thraquinone and anilin. Crimsonred. ble. Crimsonred Crimson red. Crimsonred.

Crimson red.

Bromin derivative from conden- Dark violet Slightly sol- Rather solu- Readily sol- Readily sol- Readily sol- Dirty -gray sat-ion product of 1.3-dinitro-anuble. e. uble. uble. uble. brown. thraquinone and anilin. Cherry red. Cherry red. Violet red. Violet red. Intenscdviot re Ilroinin derivative from conden- Violet Dil'iicultly Some what Rather eas- Rather cas- Readily sol- Olive green.

sation product of 1. 8-dinitro-ansoluble. more easilysoluhle. ily soluble. uble. thraquinone and amlin. Crimson red. ily soluble. Cherry red. Cherry red. Cherry red.

. Crimson red.

Broinin derivatix'e from eondeu- Brick red Insoluble Hardly solu- Ratherdifii- Rather eas- Readily sol- Y e l l o w sation product of 1.5-dinitro-an- Yellow red. ble. cultly solily soluble. uble. brown. thraquinone and para-toluidin. Yellow red. uble. Crimson red. Crimson red.

Crimson red.

Broiuiu derivative from conden- Violet brown Slightly sol- Somewhat 10 do -(l0 Brownish satiou product oi 1.5-dinitro-anuble. soluble. Olive. thraquinoneandorthotoluidin. Crimson red. Crimsonred.

Bromin derivative from conden- Gray violet Almost in- Only slight- Slightly sol- Rather solu- Soluble O l i v e sation product of 1.54linitro-ansoluble. 1y soluble. uble. e. Cherry red. brown. thraquinone and benzidin. Violet. Violet. Red violet. Red violet.

Brornin derivative from condcn- Red brown Almost in- Hardly sol- Very slight- Slightly sol- Rathersohr Dirtyviolvt.

sation product of 1.5-diuitro-ansoluble. uble, with ly soluble. uble. ble. thraquinone and alpha-naphreddish Red brown. Rod brown. Brow nish ihylamin. color. red.

Chlorin derivative froin conden Violet brown Rather eas- Easily solu- Rathersolu- Easily solu- Readily sol- Discolorcd sation product ot 1.5:dnntro an ilysolnble. ble. ble. ble. uble. brownish. tlnlarx uinone and amhn. Prod- Cherry red. Cherry red. Cherry red. Cherry red. Cherry red.

Chlorin derivatix'e from conden- Palcbrickrcd Readily sol- Readily sol- Readily sol- Readily sol- Readily sol- Y e l l o w sation product ot 1.4:d nntro-anuhle. uble. uble. uble. uble. brown. thraquinone and anlhn. Prod- Y e l l o w Y e 1 1 o w {Y e 11 0 w Y e l l o w Red brown. uct B. brown. brown. b r o w n b 1' o w n with redwith reddish cast. dish cast.

I would remark wit-h reference to the nomenclature adopted in this specification that by 1. S-dinitro-anthraquinone I mean that one which corresponds to chrysazine and by 1.3- dinitro anthraquinone I mean that body which corresponds to xanthopurpurinc.

Now what I claim is 1. The process for the production of new halogen derivatives of alphylated diamidoanthraquinones by treating them with the herein-described halogens in the presence of a solvent herein described.

2. As a new article of manufacture the halogen derivatives of alphylated amido-anthraquinones which can be obtained from the herein-described halogens and alphylated amidoanthraquinones and which are soluble in benzene, and on heating with an alin are converted into a green coloring-matter, all substantially as described.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

OSCAR RALLY.

Witnesses:

ERNEST F. EHRHARDT, J. L. HEINKE. 

